Solution containment during buffer layer deposition

ABSTRACT

Improved methods and apparatus for forming thin-film layers of chalcogenide on a substrate web. Solutions containing the reactants for the chalcogenide layer may be contained substantially to the front surface of the web, controlling the boundaries of the reaction and avoiding undesired deposition of chalcogenide upon the back side of the web.

CROSS-REFERENCE TO RELATED APPLICATION

This application claims priority under 35 U.S.C. §119 and applicableforeign and international law of U.S. Provisional Patent ApplicationSer. No. 61/068,458, filed on Mar. 5, 2008, which is hereby incorporatedby reference in its entirety.

BACKGROUND

The field of photovoltaics generally relates to multi-layer materialsthat convert sunlight directly into DC electrical power. The basicmechanism for this conversion is the photovoltaic (or photoelectric)effect, first correctly described by Einstein in a seminal 1905scientific paper for which he was awarded a Nobel Prize for physics. Inthe United States, photovoltaic (PV) devices are popularly known assolar cells. Solar cells are typically configured as a cooperatingsandwich of p-type and n-type semiconductors, in which the n-typesemiconductor material (on one “side” of the sandwich) exhibits anexcess of electrons, and the p-type semiconductor material (on the other“side” of the sandwich) exhibits an excess of holes, each of whichsignifies the absence of an electron. Near the p-n junction between thetwo materials, valence electrons from the n-type layer move intoneighboring holes in the p-type layer, creating a small electricalimbalance inside the solar cell. This results in an electric field inthe vicinity of the junction.

When an incident photon excites an electron in the cell into theconduction band, the excited electron becomes unbound from the atoms ofthe semiconductor, creating a free electron/hole pair. Because, asdescribed above, the p-n junction creates an electric field in thevicinity of the junction, electron/hole pairs created in this mannernear the junction tend to separate and move away from junction, with theelectron moving toward the n-type side, and the hole moving toward thep-type side of the junction. This creates an overall charge imbalance inthe cell, so that if an external conductive path is provided between thetwo sides of the cell, electrons will move from the n-type side back tothe p-type side along the external path, creating an electric current.In practice, electrons may be collected from at or near the surface ofthe n-type side by a conducting grid that covers a portion of thesurface, while still allowing sufficient access into the cell byincident photons.

Such a photovoltaic structure, when appropriately located electricalcontacts are included and the cell (or a series of cells) isincorporated into a closed electrical circuit, forms a working PVdevice. As a standalone device, a single conventional solar cell is notsufficient to power most applications. As a result, solar cells arecommonly arranged into PV modules, or “strings,” by connecting the frontof one cell to the back of another, thereby adding the voltages of theindividual cells together in electrical series. Typically, a significantnumber of cells are connected in series to achieve a usable voltage. Theresulting DC current then may be fed through an inverter, where it istransformed into AC current at an appropriate frequency, which is chosento match the frequency of AC current supplied by a conventional powergrid. In the United States, this frequency is 60 Hertz (Hz), and mostother countries provide AC power at either 50 Hz or 60 Hz.

One particular type of solar cell that has been developed for commercialuse is a “thin film” PV cell. In comparison to other types of PV cells,such as crystalline silicon PV cells, thin film PV cells require lesslight-absorbing material to create a working cell, and thus can reduceprocessing costs. Thin film based PV cells also offer improved cost byemploying previously developed deposition techniques widely used in thethin film industries for protective, decorative, and functionalcoatings. Common examples of low cost commercial thin film productsinclude water permeable coatings on polymer-based food packaging,decorative coatings on architectural glass, low emissivity thermalcontrol coatings on residential and commercial glass, and scratch andanti-reflective coatings on eyewear. Adopting or modifying techniquesthat have been developed in these other fields has allowed a reductionin development costs for PV cell thin film deposition techniques.

Furthermore, thin film cells, particularly those employing a sunlightabsorber layer of copper indium diselenide, copper indium disulfide,copper indium aluminum diselenide, or copper indium gallium diselenide,have exhibited efficiencies approaching 20%, which rivals or exceeds theefficiencies of the most efficient crystalline cells. In particular,copper indium gallium diselenide (CIGS) is stable, has low toxicity, andis truly thin film, requiring a thickness of less than two microns in aworking PV cell. As a result, to date CIGS appears to have demonstratedthe greatest potential for high performance, low cost thin film PVproducts, and thus for penetrating bulk power generation markets.

Thin film PV materials may be deposited either on rigid glasssubstrates, or on flexible substrates. Glass substrates are relativelyinexpensive, generally have a coefficient of thermal expansion that is arelatively close match with the CIGS or other absorber layers, and allowfor the use of vacuum deposition systems. However, such rigid substratessuffer from various shortcomings, such as a need for substantial floorspace for processing equipment and material storage, specialized heavyduty handling equipment, a high potential for substrate fracture,increased shipping costs due to the weight and delicacy of the glass,and difficulties in installation. As a result, the use of glasssubstrates is not optimal for large-volume, high-yield, commercialmanufacturing of multi-layer functional thin film materials such asphotovoltaics.

In contrast, roll-to-roll processing of thin flexible substrates allowsfor the use of compact, less expensive vacuum systems, and ofnon-specialized equipment that already has been developed for other thinfilm industries. PV cells based on thin flexible substrate materialsalso exhibit a relatively high tolerance to rapid heating and coolingand to large thermal gradients (resulting in a low likelihood offracture or failure during processing), require comparatively lowshipping costs, and exhibit a greater ease of installation than cellsbased on rigid substrates.

A particular type of n-type semiconductor material that may be used inthin-film PV cells is known in the field of chemistry as a chalcogenide.A chalcogenide is a chemical compound consisting of at least onechalcogen ion and at least one more electropositive element such as ametal. Forming a thin film of chalcogenide is described in the priorart, for example, in U.S. Pat. No. 6,537,845 to McCandless et al., whichis hereby incorporated into the present disclosure by reference for allpurposes. However, forming chalcogenide films having a desired thicknessand uniformity remains technically challenging and improvements areneeded.

Historically, the formation of a thin-film chalcogenide buffer layer orlayers often proceeds by a relatively inefficient cyclical process thatincludes heating the substrates in a water-containing vessel to anelevated temperature, adding and mixing in a metallic salt, and thenadding and mixing in a chalcogen-containing component. After aproscribed time at a proscribed temperature, the reaction is complete,the substrates are removed, the used solution is sent to wastetreatment, reactant-containing solution is applied to the web, and thevessel is cleaned for the next reaction. In addition, existing methodsof applying the reactant-containing solution to the web typically resultin deposition of chalcogenide over both the desired (“front” or “top”)surface of the web, and also over at least a portion of the other(“back” or “bottom”) surface of the web, requiring at least one cleaningstep to remove the material from the back surface. This is typicallyaccomplished with an acidic solution that must be carefully controlledand completely removed to avoid damage to the desired thin-film layersand to avoid long-term corrosion issues activated by the presence ofresidual acidity.

Furthermore, when reactant solutions reach the back side of thesubstrate, either because the entire substrate is immersed in a bath ofreactant solution, or because solutions applied to the top side of thesubstrate are insufficiently contained on the top side, it may bedifficult or impossible to remove all of the excess chalcogenide thatforms on the back of the substrate and/or any heating elements. This canaffect the amount of heat reaching the top of the substrate. Forexample, chalcogenide build-up on the underside of the substrate mayaffect the heat capacity of the substrate and its thermal conductivity,and chalcogenide build-up on the heaters may affect the emissivityand/or thermal conductivity of the heaters. Furthermore, these effectsmay be non-uniform across the width of the substrate.

Such undesirable chalcogenide deposition on the underside of thesubstrate and/or on any heating elements disposed on that side of thesubstrate may result in a poorly controlled substrate temperature andthe corresponding formation of a chalcogenide buffer layer havingundesirable characteristics. For example, if the amount of heat reachingthe top surface of the substrate is decreased due to chalcogenideformation under the substrate, this may result in the formation of anundesirably thin chalcogenide buffer layer on the top surface.Similarly, if the amount of heat reaching the top surface of thesubstrate is non-uniform due to non-uniform chalcogenide formation underthe substrate, this may result in the formation of an undesirablynon-uniform chalcogenide buffer layer on the top surface. These effectsmay be difficult to control due to unpredictable and uncontrolledchalcogenide formation under the substrate.

It is known in the art to deposit a chalcogenide layer on a substrateweb in a roll-to-roll process and to raise the lateral edges of thesubstrate web, for example by draping the web edges over vertical rails,to improve solution containment. However, this typically leads toundesirable buckling forces on the web, making it difficult to maintaina desired degree of flatness in the deposition region. At the same time,previous systems used a hold-down mechanism such as one or more wheelsto keep the web in contact with an underlying surface such as aconductive heater. However, this creates local hot spots on thesubstrate, resulting in undesirable nonuniformities in the chalcogenidelayer. It is also known in the art to tilt the entire web longitudinallyto control the depth of reactant solutions on the web. However, theseprior systems do not provide for multiple slope adjustments in variousportions of the deposition region, and thus may not provide sufficientcontrol over the solution depth and the corresponding chalcogenidethickness. For all of the above reasons, improved methods and apparatusfor containing chalcogenide reactants to the front or top surface of asubstrate are desirable.

SUMMARY

The present teachings disclose improved methods and apparatus forforming thin film layers of chalcogenide on a substrate web. Accordingto the present teachings, solutions containing the reactants for thechalcogenide layer may be contained substantially to the front surfaceof the web, avoiding undesired deposition of chalcogenide upon the backside.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a top view of a thin film photovoltaic cell, according toaspects of the present disclosure.

FIG. 2 is a schematic side view of an apparatus for forming a thin-filmlayer on a substrate web.

FIG. 3 is a partial sectional view of a transport roller with a concavetransverse profile lifting transverse edge portions of a substrate webwhile supporting and transporting the web.

FIG. 4 is a partial sectional view of a transverse lifting structurewith a concave transverse profile lifting transverse edge portions of asubstrate web while supporting the web.

FIG. 5 is a partial sectional view of frustoconical bearing surfaceslifting transverse edge portions of a substrate web.

FIG. 6 is a partial section view of angled lifting structures disposedat the transverse edges of a transport roller and supporting thetransverse edge portions of a substrate web.

FIG. 7 is a partial sectional view of angled lifting structures disposedin front of a transport roller and supporting the transverse edgeportions of a substrate web.

FIG. 8 is a partial side elevational view of transverse edge portions ofa substrate web being lifted by frustoconical bearing surfaces, whilethe web is transported by transport rollers.

FIG. 9 is a side view showing details of a hold-down structureconfigured to hold a substrate web in contact with an underlyingtransport mechanism.

FIG. 10 is a perspective view showing a pair of hold-down structuresholding a substrate web in contact with an underlying transportmechanism.

FIG. 11 is a schematic plan view of portions of an apparatus fortransporting a substrate web through a deposition region, showing therelative arrangement of transport rollers, lifting structures, andhold-down mechanisms.

FIG. 12 is a flow chart depicting a method of forming a thin filmchalcogenide buffer layer on a substrate web.

DETAILED DESCRIPTION I. Introduction

Manufacture of flexible thin-film PV cells may proceed by a roll-to-rollprocess. As compared to rigid substrates, roll-to-roll processing ofthin flexible substrates allows for the use of relatively compact, lessexpensive vacuum systems, and of some non-specialized equipment thatalready has been developed for other thin-film industries. Flexiblesubstrate materials inherently have lower heat capacity than glass, sothat the amount of energy required to elevate the temperature isminimized. They also exhibit a relatively high tolerance to rapidheating and cooling and to large thermal gradients, resulting in a lowlikelihood of fracture or failure during processing. Additionally, onceactive PV materials are deposited onto flexible substrate materials, theresulting unlaminated cells or strings of cells may be shipped toanother facility for lamination and/or assembly into flexible or rigidsolar modules. This strategic option both reduces the cost of shipping(lightweight flexible substrates vs. glass), and enables the creation ofpartner-businesses for finishing and marketing PV modules throughout theworld.

One or more of the layers deposited in a thin-film PV cell typically isa “window layer(s)” that allows usable light to penetrate to theinterior of the cell, and which in some cases also may serve as then-type semiconductor material in the cell. Such a layer also may bereferred to in the PV cell field as a “buffer layer.” When used both asa window layer and a semiconductor, the buffer layer ideally should beboth substantially transparent to light in a desired wavelength range,and also exhibit the appropriate electronic properties. The buffer layeralso could consist of multiple window layers acting also assemiconductors, such as a layer of cadmium sulfide followed by a layerof cadmium-zinc sulfide. A thin-film buffer layer with desiredproperties may be formed through chemical reaction between one or moremetals such as zinc, cadmium, lead, mercury, or any metal or combinationof metals selected from groups 1b, 2b, or 3a of the Periodic Table ofthe Elements, and a chalcogen such as oxygen, sulfur, selenium, ortellurium. The resulting compounds are often termed chalcogenides.Suitable window or buffer layer compounds for solar devices may include,for example, cadmium sulfide, zinc sulfide, zinc selenide, cadmium zincselenide, zinc oxide, and cadmium zinc oxide.

FIG. 1 shows a top view of a thin-film photovoltaic cell 10, inaccordance with aspects of the present disclosure. Cell 10 issubstantially planar, and typically rectangular as depicted in FIG. 1,although shapes other than rectangular may be more suitable for specificapplications, such as for an odd-shaped rooftop or other surface. Thecell has a top surface 12, a bottom surface 14 opposite the top surface,and dimensions including a length L, a width W, and a thickness. Thelength and width may be chosen for convenient application of the cellsand/or for convenience during processing, and typically are in the rangeof a few centimeters (cm) to tens of cm. For example, the length may beapproximately 100 millimeters (mm), and the width may be approximately210 mm, although any other suitable dimensions may be chosen. The edgesspanning the width of the cell may be characterized respectively as aleading edge 16 and a trailing edge 18. The total thickness of cell 10depends on the particular layers chosen for the cell, and is typicallydominated by the thickness of the underlying substrate of the cell. Forexample, a stainless steel substrate may have thickness on the order of0.025 mm (25 microns), whereas all of the other layers of the cell mayhave a combined thickness on the order of 0.002 mm (2 microns) or less.

Cell 10 is created by starting with a flexible substrate, and thensequentially depositing multiple thin layers of different materials ontothe substrate. This assembly may be accomplished through a roll-to-rollprocess whereby the substrate travels from a pay-out roll to a take-uproll, traveling through a series of deposition regions between the tworolls. The PV material then may be cut to cells of any desired size. Thesubstrate material in a roll-to-roll process is generally thin,flexible, and can tolerate a relatively high-temperature environment.Suitable materials include, for example, a high temperature polymer suchas polyimide, or a thin metal such as stainless steel or titanium, amongothers. Sequential layers typically are deposited onto the substrate inindividual processing chambers by various processes such as sputtering,evaporation, vacuum deposition, chemical deposition, and/or printing.These layers may include a molybdenum (Mo) or chromium/molybdenum(Cr/Mo) back contact layer; an absorber layer of material such as copperindium diselenide, copper indium disulfide, copper indium aluminumdiselenide, or copper indium gallium diselenide (CIGS); a buffer layeror layers such as a layer of cadmium sulfide (CdS); and a transparentconducting oxide (TCO) layer acting as the top electrode of the PV cell.In addition, a conductive current collection grid, usually constructedprimarily from silver (Ag) or some other conductive metal, is typicallyapplied over the TCO layer.

Although the precise thickness of each layer of a thin-film PV celldepends on the exact choice of materials and on the particularapplication process chosen for forming each layer, exemplary materials,thicknesses and methods of application of each layer described above areas follows, proceeding in typical order of application of each layeronto the substrate:

Layer Exemplary Exemplary Exemplary Method Description MaterialThickness of Application Substrate Stainless steel 25 μm N/A (stockmaterial) Back contact Mo 320 nm  Sputtering Absorber CIGS 1700 nm Evaporation Buffer CdS 80 nm Chemical deposition Front electrode TCO 250nm  Sputtering Collection grid Ag 40 μm PrintingThe remainder of this disclosure focuses on various methods andapparatus for forming chalcogenide buffer layer(s).

II. Solution Containment and Web Transport

This section describes methods and apparatus for transporting a web ofsubstrate material through a deposition region, and for containingvarious reactant solutions that include chemical components of a bufferand/or window layer within a desired region of the web.

According to aspects of the present disclosure, a buffer layer may beapplied to the underlying PV cell layers (typically a bottom substratelayer, one or more back contact layers, and an absorber layer) via achemical deposition process. As shown in FIG. 2, the process involves anapparatus, generally indicated at 30, for transporting a web 32 ofthin-film substrate material through a deposition region 34 in alongitudinal direction, and dispensing one or more reactant solutions 36onto the web within the deposition region. To react and form a suitablechalcogenide, the reactant solution should contain, at a minimum, atleast one metal and at least one chalcogen. In addition, the solutiontypically will contain a chemical complexant such as ammonia, anddeionized water (DI).

Although the system depicted in FIG. 2 transports the web linearly andin a direction corresponding to the longitudinal dimension of the web,the present teachings also contemplate alternative methods of depositinga thin film buffer layer. These alternatives include, for example,solution application onto a concave or convex web disposed on the insideor outside of a drum-like structure, and horizontal web transport usingone or a plurality of weirs (such as containers, plates, or rollers)held to a “controlled-drainage” distance from the web to hold thechalcogenide solution against the web for a suitable reaction period.

Apparatus 30 includes a transport mechanism, generally indicated at 40,for conveying a continuous flexible web of substrate material throughthe deposition region in the longitudinal region. Transport mechanism 40may take various forms, such as one or more continuous belts that mayconvey the web while supporting it either from above or below, or aseries of rollers upon which the web rests and is conveyed. FIG. 2depicts a transport mechanism that includes a plurality of synchronizedtransport rollers 42 that both support the substrate web and transportit. Rollers 42 may be evenly spaced, as shown in FIG. 2, or they may beunevenly spaced to accommodate other desired elements of the apparatus.To ensure that the web is transported through the deposition region at auniform speed along its length, rollers 42 may be synchronized by anysuitable method. For example, the rollers all may be driven by a singlerotating shaft, with each roller linked to the common shaft. The rollersmay be linked to the shaft by a standard gear/screw linking mechanism(not shown) or by any other linking mechanism. In some cases, thesupport rollers may not rotate at all, but rather may be stationary,precision leveled cross pieces. In other cases, the support rollers maybe rotatable but not driven, in which case the pay-out and/or take-upmechanisms may drive the motions of the substrate web.

In many existing systems for chemically synthesizing a chalcogenidebuffer layer via a chemical bath, dispensing the solutions onto the webtypically results in desirable deposition of the buffer layer over boththe top (or front) side of the web, as well as undesirable depositionover some or all of the bottom (or back) of the web. This undesirabledeposition may require a subsequent cleaning step with an acidicsolution, as well as a possible second additional cleaning step toremove the residual acid used to clean the excess buffer layer in thefirst cleaning step. During these additional cleaning steps, it may benecessary, and can be difficult, to protect the top-side buffer layerand the other, previously deposited thin film layers on the top side ofthe web from attack by the active solutions used in the cleaning. Theuse of sacrificial or reusable protective backing material or webs hasbeen considered, but has its own limitations and added costs.

According to the present teachings, and as depicted in FIG. 3, opposingtransverse edge portions 44 of the substrate 32 may be liftedsufficiently by a lifting mechanism, generally indicated at 46. Liftingmechanism 46 is configured to lift edge portions 44 of the web, relativeto a central portion 48 of the web, by an amount sufficient to containthe buffer reactant solutions substantially upon the top surface of theweb. This may be accomplished in various ways. For example, as shown inFIG. 3, the lifting mechanism may include one or more transport rollers42 having concave edge portions, so that lifting the transverse edgeportions of the web is accomplished simply by passing the web over theconcave transverse profile of the concave roller(s). In suchembodiments, the transport rollers may serve the dual purposes of bothtransporting the web at a uniform speed, and containing the bufferreactant solutions upon the top surface of the web within the depositionregion or any other desired longitudinal region.

Alternatively, opposing transverse edge portions of the web may belifted by a lifting mechanism that includes dedicated liftingstructures, the primary purpose of which is to support the web edges andcontain the buffer reactant solutions, rather than to transport the web.For example, as depicted in FIG. 4, the dedicated lifting structures mayinclude transverse lifting structures 50 that extend substantiallyacross the transverse dimension of the web in a fashion similar totransport rollers 42, but that do not function as transport rollers.Transverse lifting structures 50 have a concave transverse profile, toshape the transverse profile of the web sufficiently to contain anydeposited solutions, but do not rotate. Lifting structures 50 may bedisposed longitudinally, for example, between two of transport rollers42, or may replace one or more of the rollers depicted in FIG. 2.

Many other lifting mechanisms are within the scope of the presentteachings. For example, as shown in FIG. 5, lifting the web edges may beaccomplished by contacting opposing transverse edge portions of the webwith one or more bearing surfaces 52, which may or may not be rotatable.To lift the edge portions, the bearing surfaces typically will bedisposed slightly within the transverse boundaries of the web. Bearingsurfaces 52 may be approximately frustoconical as depicted in FIG. 5, oralternatively, the bearing surfaces may be spherical, cylindrical, orany other shape suitable for sufficiently lifting and supporting theedge portions of the web. For example, complex-shaped bearing surfacesmay be used that have more than one slope, and/or that have a concavegeometry. In some embodiments, shapes having both an inward and anoutward camber may be advantageous. Furthermore, a relatively shallowslope, or multiple/continuous slopes may be less sensitive to web edgevariations, while still maintaining containment of the reactingsolution. Regardless of their construction, the bearing surfaces may bedisposed anywhere along the longitudinal dimension of the web, andtypically will be disposed either within, or in proximity to, thedeposition region. For example, as depicted in FIG. 8, two opposingpairs of bearing surfaces may be disposed between adjacent transportrollers.

As depicted in FIG. 6, the lifting mechanism may include angled edgeportions or bearing surfaces 52′ attached to one of transport rollers42. Although similar in many respects to the lifting mechanism depictedin FIG. 3, the mechanism depicted in FIG. 6 may have a simplerconstruction because angled edge portions 52′ can be manufacturedseparately from cylindrical transport rollers 42. FIG. 7 depicts yetanother alternative, where dedicated lifting structures 52″ includeangled edge portions configured to lift the transverse edge portions ofthe substrate web. As in the case of bearing surfaces 52 depicted inFIG. 5, lifting structures 52″ are not attached directly to transportrollers 42, but rather may be disposed, for example, between adjacentrollers and supported by a separate support structure as shown in FIG.8.

It should be appreciated that all of the lifting mechanisms depicted inFIGS. 3-8 include lifting structures shaped to conform to the liftededge portions of the substrate web. For example, the lifting structuresdepicted in FIGS. 3-4 include concave lifting portions at theirtransverse edges, and the lifting structures depicted in FIGS. 5-7include substantially planar lifting portions angled away from thecentral portion of the substrate web. In contrast, some prior artlifting mechanisms used vertical rails or bars, which are not shaped toconform to the lifted edge portions, to lift the substrate edges.Matching the shape of the lifting structures to the shape of the liftededge portions may, for example, provide a small amount of friction thatdecreases the tendency of the central portion of the web to buckle orotherwise deviate from substantial flatness, which leads to lesssolution overflow, a more uniform solution layer on the substrate, and acorrespondingly more uniform chalcogenide layer.

Lifting the transverse edge portions of the web may be performed in afixed amount, or the lift may be adjustable within a range of liftamounts. In embodiments using dedicated lifting structures disposed nearthe transverse boundaries of the web, such as structures 52 and 52″depicted in FIGS. 5 and 7, respectively, any desired lift adjustment maybe accomplished simply by adjusting the height of the liftingstructures. In embodiments using either dedicated lifting structures ortransport rollers that extend across the transverse dimension of the weband that have a concave transverse profile, the lift adjustment may beaccomplished by altering the transverse profile of the lifting structureor roller. For example, if the concave dedicated lifting structures orconcave transport rollers are segmented in the transverse dimension, theheight of various segments may be adjusted individually or in groups,until a desired transverse profile is attained to provide a desiredamount of lift of the edge portions of the web relative to a centralportion of the web.

To maintain a relatively flat profile across the central portion of theweb, which may be desirable to achieve substantial uniformity of adeposited buffer layer, the web may be held down and/or under tension atone or more positions. One convenient way to accomplish this is to holdthe web in contact with at least a subset of the transport rollers orother transport mechanism. For instance, as depicted in FIGS. 9-10, theweb may be passed underneath a plurality of hold-down rollers or wheels54 (or any other structures configured to hold the web in contact withthe transport mechanism), where each hold-down wheel is configured tohold the web in contact with a portion of an associated one of thetransport rollers 42. The hold-down structures, such as wheels orrollers, may be disposed near each edge portion of each transport rolleror, as FIG. 10 shows, the hold-down structures may be disposed in analternating arrangement, with one hold-down wheel disposed near a singleedge portion of each transport roller. In general, any arrangement ofthe hold-down structures may be suitable, provided that the structuresare sufficient to hold the web under sufficient tension so that itscentral portion maintains a desired transverse profile.

Aside from exerting downward forces to hold the web in contact with thetransport rollers, the hold-down structures may have various otheruseful features. For instance, as depicted in FIG. 9, the hold-downstructures may be counter-weighted wheels 54 mounted on shafts 56 havingintermediate pivots 58. A counterweight 60 of each structure may beadjustable within a recess 62, such that moving the counterweight in theproximal direction (toward wheel 54) increases the force of the wheelagainst the web, whereas moving the counterweight in the distaldirection (away from wheel 54) decreases the force of the wheel againstthe web. This mechanism thus supplies an adjustable downward force tothe web, to offset the upward force of the lifting mechanism on the web.Alternatively, the hold-down wheels may provide a controllable orpredetermined pressure either pneumatically or by any other suitablemechanism. Furthermore, other structures may be used to provide acontrolled hold-down pressure to the web, such as a pressurized Teflontube/gasket mounted on a fixed structure, pairs of low-friction stripsor brackets disposed above and below the web, or magnets disposed belowthe web.

In addition, as depicted in FIGS. 9-10, the wheels or rollers of thehold-down structures may be angled slightly outwardly from top tobottom, to supply a force to the web that has both a downward and anoutward component relative to the central portion of the web. Theoutward component of force, when exerted at opposing edge portions ofthe web, supplies lateral tension to the web and thus helps to hold thecentral portion of the web flat, which in turn facilitates a relativelyeven distribution of the buffer layer reactants (and thus, of the bufferlayer itself) across the transverse dimension of the web. Furthermore,the hold-down wheels may be angled slightly inwardly or outwardlyrelative to the longitudinal dimension of the web, either of which alsomay provide helpful outward forces to the web. Both of theaforementioned angles may be adjustable to some extent, to allow forvariation of the side-to-side tension in the web and/or the transverseprofile of the web.

FIG. 11 is a schematic plan view of portions of an apparatus fortransporting a substrate web (not shown) through a deposition region,showing the relative arrangement of transport rollers 42, liftingstructures 52, and hold-down mechanisms 54. Although FIG. 11 depictslifting structures 52 in the form of vertical-axis, frustoconicalbearing surfaces, it should be understood that these may be replacedwith lifting structures of various other shapes, such as those depictedin FIG. 4, 6 or 7. The lifting structures each may, for example, includea concave lifting portion, a substantially planar lifting portion angledaway from the central portion of the web, or some other structure shapedto conform to the lifted edge portions of the web. To provide a desiredamount of lift, each lifting structure may have a vertical position thatis adjustable within a range of lift amounts. As FIG. 11 depicts, thelifting structures may be disposed between adjacent transport rollers42, and may be provided as pairs of structures at each transverse edgeportion of the apparatus. Alternatively, as depicted for example inFIGS. 3 and 6, the lifting structures may be formed integrally with orconnected directly to the transport rollers, or as depicted for examplein FIG. 4, the lifting structures may be dedicated structures thatextend substantially across the transverse dimension of the substrateweb without functioning as transport rollers.

Lifting one or more edge portions of the web may be performed inresponse to a measured property of the thin film buffer layer formed bythe reactant solutions. For example, the amount of lift on one or bothsides of the web may be adjusted in response to a measurement of theuniformity of the thin film buffer layer. If the buffer layer ismeasured to be asymmetrically disposed across the transverse dimensionof the web, then the amount of lift on just one side may be adjusteduntil substantial symmetry of the buffer layer is restored. If thebuffer layer is measured to be sufficiently symmetric, but isundesirably thick toward the center of the transverse dimension of theweb, undesirably thin toward the edges of the transverse dimension ofthe web, or vice versa, then the amount of lift on both sides may beadjusted until greater transverse uniformity of the buffer layerthickness is attained. Similarly, the amount of lift on one or bothsides of the web may increased as necessary to contain the reactantsolutions, if a measurement (or mere visual inspection) indicates thatone or more of the solutions is not being sufficiently contained to thetop surface of the web.

FIG. 12 is a flow chart depicting a method, generally indicated at 100,of depositing a thin film chalcogenide buffer layer onto a flexiblesubstrate. At step 102, a web of thin-film substrate material istransported through a deposition region in a longitudinal direction. Asdescribed previously, the substrate material may include a basesubstrate, such as a thin sheet of stainless steel, upon which one ormore thin-film layers have already been deposited. For example, a backcontact layer constructed from an electrically conductive material suchas molybdenum, and a p-type semiconductor photon absorber layerconstructed from a material such as CIGS, may already have beendeposited on the base substrate. It should be understood that thesubstrate web may include these layers when it is transported throughthe deposition region. The web will generally be transported in aroll-to-roll or other similar process, in which case the longitudinaldirection will be the direction of travel between the pay-out roll andthe take-up roll.

At step 104, a metal-containing solution and a chalcogen-containingsolution are dispensed onto the top surface of the substrate web. Themetal-containing solution contains a metal known to react with achalcogen to form chalcogenide, and thus will generally be selected fromthe group consisting of copper, silver, gold, zinc, cadmium, mercury,lead, boron, aluminum, gallium, indium, and thallium. Thechalcogen-containing solution contains a chalcogen selected from thegroup consisting of oxygen, sulfur, selenium and tellurium, and which isknown to react with the metal in the metal-containing solution to form achalcogenide with desired optical and/or electronic properties. Oneexemplary combination is for cadmium to combine with sulfur to producecadmium sulfide, but other chalcogenides may be suitable as bufferlayers and/or n-type semiconductor layers. Prior to or as part of step104, the substrate web may be rinsed with deionized water or some othersuitable solution. This rinsing may remove surface irregularities orother artifacts left over from a prior deposition process (such as CIGSdeposition), and thus provide a relatively more consistent surface forchalcogenide deposition.

It should be appreciated that the metal-containing solution and thechalcogen-containing solution may be dispensed at any desiredposition(s) within the deposition region. For example, the solutions maybe dispensed together by a single dispenser 38, as depicted in FIG. 2,or the solutions may be dispensed by separate dispensers. Thesedispensers may be separated by a sufficient distance in the longitudinaldirection, such as one inch or more, to allow appreciable surface ionexchange between the metal in the metal-containing solution and anunderlying layer of photovoltaic material, in a region between the firstposition and the second position. This may have beneficial effects uponthe electronic properties of the underlying semiconductor layer (such asa CIGS layer) of the PV cell. Alternatively, separate dispensers maydispense the reactant solutions at positions that may be substantiallycoincidental, i.e. the metal-containing solution and thechalcogen-containing solution may be dispensed separately but atsubstantially the same longitudinal position on the substrate web.

Furthermore, the metal-containing solution and/or thechalcogen-containing solution may be heated to a temperature sufficientto provide at least a substantial portion of the heat of reaction forchalcogenide formation on the web. Accordingly, the temperature of oneor both of the reactant solutions will generally be greater than thetemperature of the moving web (prior to application of the solution).For example, the metal-containing solution may be heated to atemperature in the range of 55-70 degrees Celsius, whereas prior toapplication of the reactant solutions, the web may have a temperature inthe range of 25-45 degrees Celsius.

At step 106, the transverse edge portions of the substrate web arelifted relative to a central portion of the web, to contain at leastsome of the metal-containing and chalcogen-containing solutionssubstantially upon the top surface of the web. As has been describedpreviously, this may be accomplished through the use of a liftingmechanism such as a plurality of lifting structures disposed near thetransverse edge portions of the substrate. These structures may take anysuitable form, such as those depicted in FIGS. 3-8. It may beadvantageous to configure the lifting structures to conform to the shapeof the lifted edge portions of the substrate, because this may preventlocalized forces near the edges of the substrate that could result inbuckling or other vertical nonuniformities within the central portion ofthe web.

At step 108, the central portion of the web is held substantially flat.This may be accomplished by holding selected portions of the web incontact with the underlying transport mechanism, such as underlyingtransport rollers. For example, as depicted in FIG. 10 and describedabove, holding the web in contact with the transport mechanism mayinclude passing the web underneath a plurality of hold-down wheels 54,where each wheel is configured to hold the web in contact with one oftransport rollers 42. As FIG. 10 depicts, the hold-down wheels may bedisposed above the transport rollers in an alternating arrangement, andmay be configured to supply an adjustable force having downward and/oroutward components to the substrate web. A downward component of forceserves to hold the web down near its edges, whereas an outward componentof force serves to hold the central portion of the web under tension,which may result in a greater degree, or an adjustable degree, offlatness in the central portion. Thus, to adjust the degree of solutioncontainment while maintaining substantial flatness of the centralportion of the substrate web, the amount of vertical lift of the edgesof the web, the downward hold-down force near the lifted edges, and thelateral web tension all may be adjusted.

Alternatively, holding the central portion of the web flat may beaccomplished by passing the web between one or more pairs oflongitudinal strips made from a low-friction material such as Teflon,where the strips are configured to exert a desired hold-down force orpressure to a region of the substrate. As another alternative, magnetsmay be used to exert a downward force on one or more regions of thesubstrate. Such magnets may, for example, be disposed in longitudinalstrips under the substrate, either in contact or at a known distancefrom the bottom of the web.

The disclosure set forth above may encompass multiple distinctinventions with independent utility. Although each of these inventionshas been disclosed in its preferred form(s), the specific embodimentsthereof as disclosed and illustrated herein are not to be considered ina limiting sense, because numerous variations are possible. The subjectmatter of the inventions includes all novel and nonobvious combinationsand subcombinations of the various elements, features, functions, and/orproperties disclosed herein. The following numbered claims particularlypoint out certain combinations and subcombinations regarded as novel andnonobvious. Inventions embodied in other combinations andsubcombinations of features, functions, elements, and/or properties maybe claimed in applications claiming priority from this or a relatedapplication. Such claims, whether directed to a different invention orto the same invention, and whether broader, narrower, equal, ordifferent in scope to the original numbered claims that follow, also areregarded as included within the subject matter of the inventions of thepresent disclosure.

1. A method of depositing a thin film chalcogenide buffer layer onto aflexible substrate, comprising: transporting a web of thin filmsubstrate material through a deposition region by passing the web over aplurality of transport rollers disposed within the deposition region;dispensing onto a top surface of the web a metal-containing solutioncontaining a metal chosen from the group consisting of copper, silver,gold, zinc, cadmium, mercury, lead, boron, aluminum, gallium, indium andthallium, and a chalcogen-containing solution containing a chalcogenchosen from the group consisting of oxygen, sulfur, selenium andtellurium; lifting transverse edge portions of the web relative to acentral portion of the web to contain at least a portion of themetal-containing solution and at least a portion of thechalcogen-containing solution substantially upon the top surface of theweb; and holding the central portion of the web substantially flat. 2.The method of claim 1, wherein the transport rollers are configured totransport the web out of physical contact with a web heating mechanism.3. The method of claim 1, wherein at least one of the transport rollershas concave edge portions, and wherein lifting the transverse edgeportions of the web includes passing the web over the concave edgeportions of the at least one roller.
 4. The method of claim 1, whereinholding the central portion of the web substantially flat includesholding the web in contact with the transport rollers at discretepositions within the deposition region.
 5. The method of claim 4,wherein holding the web in contact with the transport rollers includespassing the web underneath a plurality of wheels, each wheel configuredto hold the web in contact with one of the transport rollers.
 6. Themethod of claim 5, wherein the wheels are disposed above the transportrollers in an alternating arrangement.
 7. The method of claim 5, whereinthe wheels are configured to supply an adjustable force to the web. 8.The method of claim 5, wherein the wheels are configured to supply aforce having both downward and outward components to the web.
 9. Themethod of claim 1, wherein lifting the transverse edge portions includescontacting each edge portion with a lifting structure shaped to conformto the lifted edge portion.
 10. The method of claim 9, wherein eachlifting structure includes a concave lifting portion.
 11. The method ofclaim 9, wherein each lifting structure includes a substantially planarlifting portion angled away from the central portion of the web.
 12. Themethod of claim 1, wherein lifting the transverse edge portions isadjustable within a range of lift amounts.
 13. An apparatus fordepositing a thin film buffer layer onto a flexible substrate,comprising: a plurality of transport rollers disposed within adeposition region and configured to convey a continuous flexible web ofsubstrate material through the deposition region in a longitudinaldirection; at least one dispenser configured to dispense onto a topsurface of the web a metal-containing solution containing a metal chosenfrom the group consisting of copper, silver, gold, zinc, cadmium,mercury, lead, boron, aluminum, gallium, indium and thallium, and achalcogen-containing solution containing a chalcogen chosen from thegroup consisting of oxygen, sulfur, selenium and tellurium; a liftingmechanism configured to lift transverse edge portions of the webrelative to a central portion of the web to restrict at least a portionof the metal-containing solution and at least a portion of thechalcogen-containing solution substantially to the top surface of theweb; and a hold-down mechanism configured to hold the central portion ofthe web substantially flat while the transverse edge portions are beinglifted.
 14. The apparatus of claim 13, wherein the lifting mechanismincludes a plurality of lifting structures disposed adjacent to thetransverse edge portions of the web, each lifting structure having asurface configured to lift one of the transverse edge portions and toconform to the shape of the lifted portion.
 15. The apparatus of claim13, wherein the transport rollers are configured to hold the web out ofphysical contact with a web heating mechanism.
 16. The apparatus ofclaim 13, wherein the lifting mechanism includes concave edge portionsof at least one of the transport rollers.
 17. The apparatus of claim 13,wherein the lifting mechanism includes at least one lifting structuredisposed longitudinally between two of the transport rollers, extendingsubstantially across the transverse dimension of the web, and configuredto lift opposing transverse edge portions of the web.
 18. The apparatusof claim 13, wherein the hold-down mechanism includes a plurality ofwheels configured to hold the web in contact with at least a subset ofthe transport rollers at discrete positions.
 19. The apparatus of claim18, wherein the wheels are configured to exert an adjustable downwardforce on the web.
 20. The apparatus of claim 18, wherein the wheels areconfigured to exert a force on the web having both a downward componentand an outward component.